Disazo-dyestuffs and process of making same



Patented Mar. 15, 1932 JOSEPH GYR, 0F BASEL, SWITZERLAND, ASSIGNOR T0SOCIETY OF CHEMICAL INDUSTRY IN BASLE, OF BASEL, SWITZERLANDDISAZO-DYESTUFFS AND PROCESS OF MAKING SAME No Drawing. Originalapplication filed January 28, 1930, Serial No. 424,021, and inSwitzerland application filed February 2, 1929. Divided and this Thisapplication is divisional of application Serial N 0. 424,021, filedJanuary 28, 1930.

The present invention relates to the manufacture of newdisazo-dyestuftswhich are particularly suitable for the production offast and level blue and grey tints on cotton and viscose. It comprisesthe process of making the new products, the new products themselves, andthe material dyed with the said products.

The manufacture consists in coupling diazo-compounds of the naphthaleneseries which do not contain other nitrogen containing groups with aproduct of the general formula in which 00 in one case signifies ahydrogen atom and in the other case a hydrogen atom then diazotizing themono-azo-dyestuif thus obtained and coupling with certain derivatives ofthe 2-amino-5-hy droxynaphthalene, i. e. compounds of the generalformula R standing far a hydrogen atom or alkyl or a phenyl or benzylresidue directly bound to the nitrogen atom and free from N H groups.The coupling is always performed in an alkaline medium. According to thenature of the diazotized amino-azo-dyestuif the coupling is carried outeither in presence of sodium carbonate or in presence of pyridine. Amixture of sodium carbonate and pyridine may also be used. The sodiumcarbonate may wholly or in part be replaced by another alkali, forexample by ammonia. The dyestuffs thus obtained may be converted intonew February 2, 1931. Serial No. 513,054.

A similar result is attained y coupling the diazotized used as the firstdiazotizone which contains a saponifia saponifying agent.

he new dyestuffs which correspond with the general formula n I 1' 1!wherein R stands for a residue of a diazotizmg component of thenaphthalene serles containing no other nitrogen containing Example 130.3 parts of 2-aminonaphthalene-4:8-disulfonic acid are diazotized inthe usual man; ner and the diazo-compound is coupled with a hydrochloricacid solution of 18.7 parts of l-amino-2-ethoxynaphthalene. WVhencoupling is complete, a solution of 6.9 parts of sodium nitrite isgradually added at l5 20 C. The diazo-compound of the monoazodyestufl issalted out, filtered, washed with saturated common salt solution andintroduced gradually into an ice-cold solution of 23.9 parts of2-amino-5-hydroxynaphthalene- 'T-sulfonic acid in 100 parts of water and300 parts of pyridine. lVhen coupling is complete the dyestuil is saltedout, filtered, washed with saturated common salt solution and dried. Thedyestuil may also be salted out after the pyrldine has been separated,for

instance by distillation with steam. It corresponds with the formulaSOSH (PC2135 H033 NHz -N=N N N SiOsll and dyes artificial silk andregenerated cellulose equal blue tints.

The dyestufi obtained according to this example may be converted into acopper compound according to the data of Example 2 of the copendingapplication Serial No. 424,021.

Example 2 4:7.3 parts of 1-aminonaphthalene-8: 6-disulfonicacid-8-hydroXyl-toluene-sulfonic acid ester are diazotized in the usualmanner at 0 C. with 30 parts of hydrochloric acid of 30 per cent.strength and 6: 9 parts of sodium nitrite. The diazo-compound iscombined with a solution of 17.3 parts of l-amino-Q- methoxynaphthaleneand the necessary quantity of hydrochloric acid. After the coupling iscomplete the monoazo-dyestu'fif which has formed is filtered, dissolvedin the neces sary quantity of an ice-cold caustic soda solution, andfurther diazotized with 6.9 parts of sodium nitrite and 45 parts ofhydrochloric acid of 30 per cent. strength. After an hour the lightbrown diazo-compound thus formed is separated by addition of common saltand filtered. It is then slowly introduced, while stirring well, into anice-cold solution of 31.5 parts of 2-phenylaminonaphthalene-5-hydroxy-T-sulfonic acid, 15 parts of sodium carbonate, and 20 parts oftechnical pyridine in 500 parts of water. After the coupling is 1stcomponent I. Z-aminonaphthalene-G-sulfonie acid 1- G-SblllODlC acid V. 2naphthylamine 4 z 8- (lisulfonic 1 amino acid VI. 1 amino 5hydroxynaphtha G-sulfonic acid leneJ-sulfonic acid VII. 1 amino 8hydroxynaphtha lens-3: G-disulfonic acid 2nd component amino 2 methoxynaphthalene 1-amino-2-etl1oxynaplithalene 2 nietlioxynaphthalene 1 amino2 methoxynaphthalene complete the blue dyestufl formed is sepa rated byaddition of common salt and filtered. It is dissolved in 800 parts ofwater, treated at -78 C. with 60 parts of caustic soda solution of 30per cent. strength, and kept at this temperature for an hour. To thissolution there is slowly added so much hydrochloric acid that thesolution has only a very weak alkaline reaction. The dyestuil isseparated by addition of common salt. It forms, when dry, a dark powderwhich dissolves in water to a green-blue solution, dyeing cotton andregenerated cellulose green-blue tints of very good 'rastness to light.

The procedure is similar with other components. Among compounds whosediazo-compound may advantageously be used as first component may benamed aminonaphthalene derivatives which do not contain othernitrogen-containing groups, such as 2a1ninonaphthalene-(S-sulfonic acid,Q-aminonaphthalena T-sulionic acid, Q-aminonaphthalene-d: 8-disultonicacid, 1-aminonaphthalenel-sultonic acid or other sulionic acids derivingfrom the ocor the B-naphthylamine, further aminonaphtholsulfonic acidsthe Ell -group of which stands in an a-position of the one six memberedring, and the OH-group of which stands in an a-position of the othersix-menibered ring, such as l-amino fi-hydroxynaphthalene-T-sulfonicacid, 1-amino-8hydro: ynaphthalene-3: G-disuliionic acid, 1-amino-8-hydroxynaphthalenel:G-disulfonic acid, 1-amino-S-hydroxynaphthalene-a-sulfonic acid, 1 amino 8 hydroxynaphthalene2 l disulphonic acid, and the like (preferably in the form of anO-ester), and so on. As suitable middle components may be named themethyl, ethyl, propyl, butyl, etc. ethers of the l-amino-2-hydroxynaphthalene, or the 6- or T-sulfonic acids of these products.As suitable end components may be named various (methyl) phenyl,(dimethyl) -phenyl, (methoXy) -phenyl, N-hydroxyphenyL,N-hydroXyphenylcarboxylic acids, N-benzyl-, Nailkyl derivatives of2-a1nino-S-hydroxynaphthalene-7-sulionic acid.

The following table shows the shades of some of the combinations of thepresent invention:

Shade oidyeing The formula of the dyestufi VI corresponds to thefollowing and in the other for SO H or hydrogen, diazotizing themonoaZo-dyestuff thus ob- The formula of the dyestuff VII corretained,coupling the diazo-compound in an sponds to the following SOaH (])OHHoas SOaH What I claim is 1. A manufacture of disazo-dyestulfs dyeingcotton and viscose silk blueto greenishblue tints, consisting incoupling a diazo-compound of the naphthalene series which contains noother nitrogen containing groups, with a compound of the general formulaO-alkyl NIH | l x z in which a: in one case stands for hydrogen and inthe other case for SO H or hydrogen, diazotizing the monoazo-dyestuffthus obtained and coupling the diazo-compound in an alkaline medium witha compound of the general formula R signifying H, alkyl, or a phenyl orbenzyl residue directly bound to the nitrogen atom and free from N Hgroups.

2. A manufacture of disazo-dyestufls dyeing cotton and viscose silk blueto greenishblue tints, consisting in coupling a diazotized aryl-sulfonicester of an 1 S-aminonaphtholsulfonic acid, with a compound of thegeneral formula O-alkyl in which at in one case stands for hydrogenformula NH O eral formula in which R stands for H, alkyl, or a phenyl orbenzyl residue directly bound to the nitrogen atom and free from N Hgroups.

3. A manufacture of disazo-dyestuifs dyeing cotton and viscose silk blueto greenishblue tints, consisting in coupling a diazotized aryl-sulfonicester of an 1: S-aminonaphtholsulfonic acid with a compound of thegeneral (I) alky1 diazotizing the tained, coupling alkaline medium eralformula monoazo-dyestufi' thus obthe diazo-compound in an with acompound of the gen H038 NH-R formula f H038 NHR1 in which R signifiesthe residue of a diazocompound of the naphthalene series which containsno other nitrogen-containing groups, a: in one case stands for ahydrogen atom and in the other for a hydrogen atom or a sulfo-group, andR for H, alkyl, or a phenyl or benzyl residue directly bound to thenitrogen atom and free from NH groups, which products from dark powders,dissolving in water to blue to green-blue solutions, and dyeing cottonand viscose silk similar tints.

5. As a new product of manufacture the which product forms a darkpowder, dissolving in water to blue to green-blue solutions,

and dyeing cotton and viscose silk similar tints.

6. As new products of manufacture the disazo-dyestufis corresponding tothe general formula in which R signifies the residue of a diazocompoundof an 1 S'aminO-naphthol-sulfonic acid, a2 in one case stands for ahydrogen atom and in the other for a hydrogen atom or a sulfo-group, andR signifying a phenyl residue directly bound to the nitrogen atom andfree from NH groups, which products form dark powders, dissolving inwater to blue to green-blue solutions, and dyeing cotton and viscosesilk similar tints.

7. As new products of manufacture the disazo-dyestufis corresponding tothe general formula 0 alkyl S 03 o s NB-phenyl residue N=N N=N whichproducts form dark powders, dissolving in water to blue to green-bluesolutions, and dyeing cotton and viscose silk similar tints.

8. As a new azo-dyestuff corresponding product of manufacture the distothe formula which product forms a dark powder, dissolving in water toblue to green-blue solutions, and dyeing cotton and viscose silk similartints.

9. As a new product of manufacture the disazo-dyestufl' corresponding tothe formula which product forms a dark powder, dissolving in water toblue to green-blue solutions, and dyeing cotton and viscose silk similartints.

In witness whereof I have hereunto signed my name this 16th day ofJanuary, 1931. JOSEPH GYR.

